Tertiary amino-substituted thiazines

ABSTRACT

This invention relates to tertiary aminosubstituted thiazines; the process of preparing such thiazines; and uses thereof, for example, as corrosion inhibitors, microbiocides, etc.

This invention relates to tertiary amino-substituted thiazines such as4-(tertiary-aminoalkylene) substituted 1,4-thiazines of the formulae:##STR1## where the R's are hydrogen or a substituted group such as ahydrocarbon group, i.e., alkyl, etc.; and R' is a hydrocarbon group suchas alkyl, or a substituted alkyl such as hydroxyalkyl and the like; Z isS, SO, SO₂ ; and A is alkylene, alkenylene, alkinylene, etc.

Copending with this application is application Ser. No. 713,704, filedon Aug. 12, 1976, relating to Quaternaries of Tertiary Amino-SubstitutedThiazines.

When divinyl sulfone is treated with a primary amine, derivatives of1,4-thiazine-1,1-dioxide result. The compounds of this invention areprepared by reacting a divinyl sulfur compound with an organic compoundcontaining one or more primary and tertiary amino groups. The reactionof a compound containing one primary and one tertiary amino group suchas N,N dimethyl-1,3-propanediamine may be illustrated by the followinggeneral equation: ##STR2## where A is alkylene such as (CH₂)₂₋₁₀ orgreater and the R's are hydrocarbon such as alkyl, substituted alkyl,etc.

In addition one mol of an alkylimino bis-alkylamine having two primaryamino groups and one tertiary amino group such asmethyliminobispropylamine or an N,N'-bis (aminoalkylene)-di-tertiaryamine such as N,N'-bis(3-aminopropyl)-piperazine having two primaryamino groups and two tertiary amino groups reacts with two mols of adivinyl sulfur compound in a similar manner. ##STR3## The amine whichreacts with the divinyl sulfur compound contains at least one primaryamino group and at least one tertiary amino group. Thus, it may containone primary and one tertiary amino group, e.g., ##STR4## one tertiaryamino group and two primary amino groups such as ##STR5## two tertiaryand two primary amino groups such as ##STR6##

In the resulting product the primary amino group or groups become partof the thiazine ring while the tertiary amino group remains unchanged.Thus, the final product contains one or two thiazine groups and one ortwo tertiary amino groups.

Examples of the divinyl sulfur compounds are:

    CH.sub.2 ═CH--S--CH═CH.sub.2

    CH.sub.2 ═CH--SO--CH═CH.sub.2

    CH.sub.2 ═CH--SO.sub.2 --CH═CH.sub.2

Examples of compounds having one primary amino group and one tertiaryamino group include N,N-dimethyl propanediamine,N,N-diethylpropanediamine, N,N-diethylethylenediamine, N-(3-aminopropyl)diethanolamine, N-(3-piperidino) propylamine, N-(3-aminopropyl)morpholine and the like.

An example of a compound having two primary amino groups and twotertiary amino groups is N,N'-Bis(3-aminopropyl)piperazine.

In carrying out the reaction the divinyl sulfone is usually added to analcoholic solution of the amine. However any non-reactive solvent may beemployed. In some cases the amine is added to an alcoholic solution ofthe divinyl sulfone particularly when a plurality of primary aminogroups is present. The reaction is exothermic and cooling is usuallyemployed to moderate the heat of reaction. A reaction temperature ofbetween 25° and 60° C. is preferred. After addition a short period ofreflux may be employed to ensure complete reaction. The reaction productmay be isolated and purified by employing conventional techniques. Theyields of the desired products are quite excellent.

The invention may be illustrated by the following examples.

EXAMPLE 1 ##STR7##

To 102 g. (1 mol) of N,N-dimethyl 1,3-propanediamine dissolved in 150ml. of methanol was slowly added, with external cooling, 118 g. (1 mole)of divinyl sulfone. After the addition had been completed, the mixturewas heated at reflux for 1 hour. The methanol was stripped off, using arotary evaporator, leaving a viscous liquid product. The product wasdistilled in vacuo. The main portion had a B.P. of 170-172/2 mm.Recovered 176 g. of a yellow viscous liquid (80% of theory)

Analyses: Calculated for C₉ H₂₀ N₂ O₂ S(percent): N, 12.75; S, 14.54.Found (percent): N, 12.78; S, 14.37.

IR and NMR spectra were used to characterize and verify the abovestructure.

EXAMPLE 2 ##STR8##

118 g. (1 mol) of divinylsulfone was added with cooling to a solution of144.2 g. (1 mol) of N-aminopropyl morpholine in 350 ml. of methanol.After the addition had been completed, the solution was heated at refluxfor 1 hr. Methanol was removed leaving a viscous liquid thatcrystallized upon standing. The crude product was recrystallized fromethanol.

Analyses: Calculated for C₁₁ H₂₂ N₂ O₃ S: N, 10.69; S, 12.21. Found: N,10.46; S, 11.86.

EXAMPLE 3 ##STR9##

162 g. (1 mol) of N-(3-aminopropyl) diethanolamine was dissolved in 300ml. of methanol. To this solution was slowly added with cooling 118 g.(1 mol) of divinyl sulfone. The crude product was isolated and purifiedby distillation.

EXAMPLE 4 ##STR10##

To 12.8 g (0.1 mol) of 3-(N-piperidino)propylamine in 50 ml. of ethanolwas added with cooling 11.8 g. (0.1 mol) of divinylsulfone. After theaddition was completed the reaction mixture was heated at reflux for 1hr. The product was stripped of ethanol and isolated by distillation.The structure was characterized by NMR and IR spectra.

EXAMPLE 5 ##STR11##

To 116 g. (1 mol) of N,N-diethyl ethylenediamine in 350 ml. of methanolwas added with cooling 118 g. (1 mol) of divinylsulfone. After theaddition was completed the reaction mixture was heated at reflux for 1hr. The product was stripped of methanol and isolated by distillation.

EXAMPLE 6 ##STR12##

To 236.05 g. (2 mol) of divinylsulfone dissolved in 350 ml. of2-propanol was slowly added with cooling 145.0 g. (1 mol) ofmethyliminobispropylamine. After the addition had been completed, thereaction mixture was heated at reflux for 1 hour. The 2-propanol wasremoved on a rotary evaporator and the crude liquid product crystallizedupon standing. It was recrystallized from ethanol.

Analyses: Calculated for C₁₅ H₃₁ N₃ O₄ S₂ : N, 9.07; S, 16.80. Found: N,9.00; S, 16.72.

The above structure was characterized by NMR and IR spectra.

EXAMPLE 7 ##STR13##

To 100 g. (0.5 mol) of N,N'-Bis(3-aminopropyl) piperazine dissolved in200 ml. of 2-propanol was slowly added with cooling 118 g. (1 mol) ofdivinylsulfone. After the addition had been completed, the reactionmixture was heated at reflux for 1 hr. The 2-propanol was removed usinga rotary evaporator leaving a white powder. The solid was purified bywashing with acetone and recrystallized from a mixture of benzene andpetroleum ether.

Analyses: Calculated for C₁₈ H₃₆ N₄ O₄ S₂ ; N, 12.84; S, 14.68. Found:N, 12.74; S, 14.73.

USES

This invention also relates to the inhibition of corrosion, particularlythe corrosion of metals in contact with the acid solutions.

The present invention is especially useful in the acidizing or treatingof earth formations and wells traversed by a bore hole. It may also beused in metal cleaning and pickling baths which generally compriseaqueous solutions of inorganic acids such as sulfuric acid, hydrochloricacid, phosphoric acid and are useful in the cleaning and treatment ofiron, zinc, ferrous alloys, and the like.

If no corrosion inhibitor is present when the aqueous acidic solutioncomes in contact with the metal, excessive metal loss and consumption orloss of acid, and other adverse results will be experienced. There hasbeen a continuing search for corrosion inhibitors which can be usedeffectively in small concentrations, and which are economical toproduce. The need is also for corrosion inhibitors which are effectiveat high temperatures, e.g., 200° F. and above, such as are found inoperations involving acidic solutions, particularly oil-well acidizingwhere higher and higher temperatures are found as the well extendsfurther into the earth.

While the compounds of this invention are of themselves particularlygood acid corrosion inhibitors, optionally they may be blended withacetylenic alcohols, dispersing and solubilizing agents such asethoxylated phenols, alcohols, and fatty acids. They may also be blendedwith such known acid inhibitors as the quinoline or alkyl pyridinequaternary compounds or synergists such as terpene alcohols, formamide,formic acid, alkyl amine, alkylene polyamines, heterocyclic amines, andthe like.

USE IN ACID SYSTEMS

The compounds of this invention can also be employed as corrosioninhibitors for acidic systems, for example as illustrated by thepickling of ferrous metals, the treatment of calcareous earthformations, etc., as described in the following sections.

USE IN ACIDIZING EARTH FORMATIONS

The compositions of this invention can also be used as corrosioninhibitors in acidizing media employed in the treatment of deep wells toreverse the production of petroleum or gas therefrom and moreparticularly to an improved method of acidizing a calcareous ormagnesium oil-bearing formation.

It is well known that production of petroleum or gas from a limestone,dolomite, or other calcareous-magnesian formation can be stimulated byintroducing an acid into the producing well and forcing it into the oilor gas bearing formation. The treating acid, commonly a mineral acidsuch as HCl, is capable of forming water soluble salts upon contact withthe formation and is effective to increase the permeability thereof andaugment the flow of petroleum to the producing well.

CORROSION TEST PROCEDURE

In these tests the acid solutions were mixed by diluting concentratedhydrochloric acid with water to the desired concentrations.

Corrosion coupons of ASTM N-80 steel were pickled in an uninhibited 10%HCl solution for 10 minutes, neutralized in a 10% solution of NaHCO₃,dipped in acetone to remove water and allowed to dry. They were thenweighed to the nearest milligram and stored in a desiccator.

In all of the tests, a 25 cc/in² acid volume to coupon surface arearatio was used. After the desired amount of acid was poured into glassbottles, the inhibitor was added. The inhibited acid solution was thenplaced in a water bath which had been set at a predetermined temperatureand allowed to preheat for 20 minutes. After which time the coupons wereplaced in the preheated inhibited acid solutions. The coupons were leftin the acid solution for the specified test time, then removed,neutralized, rinsed, dipped in acetone, allowed to dry, and thenreweighed.

The loss in weight in grams was multiplied times a calculated factor toconvert the loss in weight to lbs/ft² /24 hrs.

The factor was calculated as follows: ##EQU1##

                  TABLE 1                                                         ______________________________________                                        Acid Corrosion Test                                                                                Dura-                                                          Conc.  Test    tion         Coupon Corrosion                            Inhib-                                                                              in     Temp.   of test                                                                             Cor-   Metal  Rate (lbs/                           itor  ppm    (°F.)                                                                          (Hrs.)                                                                              rodent Type   ft.sup.2 /day                        ______________________________________                                        Ex. 2 2000   150     6     15% HCl                                                                              N-80   0.0427                               4     2000   150     6     15% HCl                                                                              N-80   0.0511                               6     2000   150     6     15% HCl                                                                              N-80   0.0499                               7     2000   150     60    15% HCl                                                                              N-80   0.0474                               Blank --     150     6     15% HCl                                                                              N-80   0.1956                               ______________________________________                                    

USE IN BRINES

This phase of the invention relates to the prevention of corrosion insystems containing a corrosive aqueous medium, and most particularly insystems containing brines.

More particularly, this invention relates to the prevention of corrosionin the secondary recovery of petroleum by water flooding and in thedisposal of waste water and brine from oil and gas wells. Still moreparticularly, this invention relates to a process of preventingcorrosion in water flooding and in the disposal of waste water and brinefrom oil and gas wells which is characterized by injecting into anunderground formation an aqueous solution containing minor amounts ofcompositions of this invention, in sufficient amounts to prevent thecorrosion of metals employed in such operation. This invention alsorelates to corrosion inhibited brine solutions of these compounds.

When an oil well ceases to flow by the natural pressure in the formationand/or substantial quantities of oil can no longer be obtained by theusual pumping methods, various processes are sometimes used for thetreatment of the oil-bearing formation in order to increase the flow ofthe oil. These processes are usually described as secondary recoveryprocesses. One such process which is used quite frequently is the waterflooding process wherein water is pumped under pressure into what iscalled an "injection well" and oil, along with quantities of water, thathave been displaced from the formation, are pumped out of an adjacentwell usually referred to as a "producing well." The oil which is pumpedfrom the producing well is then separated from the water that has beenpumped from the producing well and the water is pumped to a storagereservoir from which it can again be pumped into the injection well.Supplementary water from other sources may also be used in conjunctionwith the produced water. When the storage reservoir is open to theatmosphere and the oil is subject to aeration this type of waterflooding system is referred to herein as an "open water floodingsystem." If the water is recirculated in a closed system withoutsubstantial aeration, the secondary recovery method is referred toherein as a "closed water flooding system."

Because of the corrosive nature of oil field brines, to economicallyproduce oil by water flooding, it is necessary to prevent or reducecorrosion since corrosion increases the cost thereof by making itnecessary to repair and replace such equipment at frequent intervals.

I have now discovered a method of preventing corrosion in systemscontaining a corrosive aqueous media, and most particularly in systemscontaining brines, which is characterized by employing the compositionsof this invention.

I have also discovered an improved process of protecting from corrosionmetallic equipment employed in secondary oil recovery by water floodingsuch as injection wells, transmission lines, filters, meters, storagetanks, and other metallic implements employed therein and particularlythose containing iron, steel, and ferrous alloys, such process beingcharacterized by employing in water flood operation the compositions ofthis invention.

This phase of the invention then is particularly concerned withpreventing corrosion in a water flooding process characterized by theflooding medium containing an aqueous or an oil field brine solution ofthese compounds.

In many oil fields large volumes of water are produced and must bedisposed of where water flooding operations are not in use or wherewater flooding operations cannot handle the amount of produced water.Most States have laws restricting pollution of streams and land withproduced waters, and oil producers must then find some method ofdisposing of the waste produced salt water. In many instances,therefore, the salt water is disposed of by injecting the water intopermeable low pressure strata below the fresh water level. The formationinto which the water is injected is not the oil producing formation andthis type of disposal is defined as salt water disposal or waste waterdisposal. The problems of corrosion of equipment are analogous to thoseencountered in the secondary recovery operation by water flooding.

The compositions of this invention can also be used in such waterdisposal wells thus providing a simple and economical method of solvingthe corrosion problems encountered in disposing of unwanted water.

Water flood and waste disposal operations are too well know to requirefurther elaboration. In essence, in the present process, the floodingoperation is effected in the conventional manner except that theflooding medium contains a minor amount of the compound of thisinvention, sufficient to prevent corrosion, in concentrations of about10 ppm to 10,000 ppm., or more, for example, about 50 to 5,000 ppm., butpreferably about 15 to 1,500 ppm. The upper limiting amount of thecompounds is determined by economic considerations. Since the success ofa water flooding operation manifestly depends upon its total cost beingless than the value of the additional oil recovered from the oilreservoir, it is quite important to use as little as possible of thesecompounds consistent with optimum corrosion inhibition. Optimumperformance is generally obtained employing about 1,000 ppm. Since thesecompounds are themselves inexpensive and are used in low concentrations,they enhance the success of a flood operation by lowering the costthereof.

In addition, these compounds are not sensitive to oxygen content of thewater and these are effective corrosion inhibitors in both open waterflooding systems and closed water flooding systems.

While the flooding medium employed in accordance with the presentinvention contains water or oil field brine and the compounds, themedium may also contain other materials. For example, the floodingmedium may also contain other agents such as surface active agents ordetergents which aid in wetting throughout the system and also promotethe desorption of residual oil from the formation, sequestering agentswhich prevent the deposition of calcium and/or magnesium compounds inthe interstices of the formation, bactericides which prevent theformation from becoming plugged through bacterial growth, tracers, etc.Similarly, they may be employed in conjunction with any of the operatingtechniques commonly employed in water flooding and water disposalprocesses, for example five spot flooding, peripheral flooding, etc.,and in conjunction with other secondary recovery methods.

Static weight loss tests--These tests are run on both synthetic andnaturally occurring fluids. The test procedure involves the measurementof the corrosive action of the fluids inhibited by the compositionsherein described upon sandblasted S.A.E. 1020 steel coupons measuring7/8×31/4 inches under conditions approximating those found in an actualproducing well, and the comparison thereof with results obtained bysubjecting identical test coupons to the corrosive action of identicalfluids containing no inhibitor.

Clean pint bottles were charged with 200 ml. of 10% sodium chloridesolution saturated with hydrogen sulfide and 200 ml. of mineral spiritsand a predetermined amount of inhibitor was then added. In all cases theinhibitor concentration was based on the total volume of the fluid.Weighed coupons were then added, the bottles tightly sealed and allowedto remain at room temperature for 3 days. The coupons were then removed,cleansed by immersion in inhibited 10% HCl, dried and weighed.

The changes in the weight of the coupons during the corrosion test weretaken as a measurement of the effectiveness of the inhibitorcompositions. Protection percentage was calculated for each test coupontaken from the inhibited fluids in accordance with the followingformula: ##EQU2## in which L₁ is the loss in weight of the coupons takenfrom inhibited fluids and L₂ is the loss in weight of coupons which weresubjected to the inhibited fluids.

                  TABLE 2                                                         ______________________________________                                        Static Weight Loss Test                                                       Example        ppm        % Protection                                        ______________________________________                                        1              1000       85.4                                                2              1000       82.6                                                3              1000       78.3                                                4              1000       77.4                                                5              1000       73.2                                                6              1000       74.1                                                7              1000       76.7                                                ______________________________________                                    

USE AS MICROBIOCIDE

Microbiocidal testing:

The screening procedure was as follows: a 1.0% by weight solution of thetest compound in water was prepared. The solution was aseptically addedto a sterile broth that would support the growth of the test organism,Desulfofivbrid desulfuricans, to provide a concentration of 25 to 100parts by weight of test compound per million parts by weight of broth. Ageneral growth medium, such as prescribed by the American PetroleumInstitute was used. The broth containing the test compound then wasdispersed in 5 cc. amounts into sterile disposable tubes and the tubeswere inoculated with the growing test organism and incubated at 35° C.for 36 hrs. The absence or presence of growth of the microorganisms wasdetermined by visual inspection by an experienced observer. Following isa summary of the results of the testing of examples of this invention.

                  TABLE 3                                                         ______________________________________                                        Microbiocidal Tests                                                                             Concentration of                                            Compound          test compound ppm                                           ______________________________________                                        Ex. 1             100                                                         Ex. 2             50                                                          Ex. 4             50                                                          Ex. 6             75                                                          Ex. 7             50                                                          ______________________________________                                    

In all of the above tests on growth of the test organism occurred, thusindicating that the compound is a biostatic or a biocide.

The amount of composition employed as corrosion inhibitor ormicrobiocide can vary widely depending on many variables such as theparticular composition employed, the particular system, the particularcorrodant or microorganism, etc. In general, one employs from about 1 to10,000 ppm or more, such as from about 10-5,000 ppm, for example fromabout 50 to 2,500 ppm, but preferably 100-1,000 ppm.

I claim:
 1. A tertiary amino-substituted thiazine having the formulaselected from the group consisting of ##STR14## where Z is SO or SO₂, Ais alkylene having 2 to 10 carbon atoms, R' is alkyl or hydroxyalkyl,##STR15## represents a cyclic amine group and ##STR16## represents acyclic diamine group.
 2. The thiazine of claim 1 having the formula##STR17## where Z is SO or SO₂, A is alkylene having 2 to 10 carbonatoms and R' is alkyl or hydroxyalkyl.
 3. The thiazine of claim 1 havingthe formula ##STR18## where Z is SO or SO₂, A is alkylene having 2 to 10carbon atoms, and ##STR19## represents a cyclic amine.
 4. The thiazineof claim 1 having the formula ##STR20## where Z is SO or SO₂, A isalkylene having 2 to 10 carbon atoms and R' is alkyl or hydroxyalkyl. 5.The thiazine of claim 1 having the formula ##STR21## Z is SO or SO₂ andA is alkylene having 2 to 10 carbon atoms.
 6. The thiazine of claim 1having the formula ##STR22##
 7. The thiazine of claim 1 having theformula ##STR23##
 8. The thiazine of claim 1 having the formula##STR24##
 9. The thiazine of claim 1 having the formula ##STR25##